Aerosol space deodorant employing certain organic peroxides

ABSTRACT

DEODORANT COMPOSITIONS COMPRISING A NORMALLY GASEOUS, LIQUEFIED PROPELLAND SAID COMPOSITION CONTAINING AS A CRITICAL INGREDIENT AND ORGANIC PEROXIDE HAVING A HALF-LIFE OF AT ;AST 10 HOURS AT 100*C.

3,828,104 AEROSOL SPACE DEODORANT EMPLOYING CERTAIN ORGANIC PEROXIDESJames Douglass Barnhurst, Millington, and Adolph Renold, Somerset, N.J.,assignors to Colgate-Palmolive Company, New York, N.Y.

No Drawing. Continuation-impart of application Ser. No.

818,042, Apr. 21, 1969, which is a continuation-inpart of applicationSer. No. 552,404, May 24, 1966, both now abandoned. This applicationOct. 26, 1971, Ser. No. 192,609

Int. Cl. A611 13/00 U.S. Cl. 42445 10 Claims ABSTRACT OF. THE DISCLOSUREDeodorant compositions comprising a normally gaseous, liquefiedpropellant said composition containig as a critical ingredient anorganic peroxide having a half-life of at least 10 hours at 100 C.

This application is a continuation-in-part of copending U.S. ApplicationSer. No. 818,042, filed Apr. 21, 1969, now abandoned, which is acontinuation-in-part of U.S. Application Ser. No. 552,404, filed May 24,1966, now abandoned.

The present invention relates to compositions useful in connection withthe dissipation of malodorous materials present in the air of enclosedspaces such as rooms, household and commercial and, more particularly,to an aerosol spray useful as a space deodorant.

Compositions and methods specifically adapted for use in the dissipationof malodorous substances commonly encountered in the household areextensively described in the prior art both patent and otherwise. Ingeneral, odor dissipation or suppression can be achieved by the use ofcompounds which, according to popular hypotheses, serve either todepress the sensitivity of the human olfactory nerve system thereby ineffect anesthetizing the sense of smell; to mask the objectionable odorby superimposing thereupon a more asthetically pleasing odor; to convertby chemical reaction, e.g., oxidation, the malodorous substances tospecies innocuous to the olfactory system or to otherwise neutralize theoffending material.

Despite the relatively widespread commercial exploitation of many of thedeodorizing agents heretofore described in the art, it has neverthelessbeen determined in practice that many of such compounds provide butmarginal advantage e.g., offsetting disadvantages detract from theoverall efiicacy of their use. Perhaps the paramount objection found toattend the use of of many of the deodorizing agents previouslypromulgated, relates to the pronounced tendency of such agents toundergo degradative decomposition being thus converted to speciestotally ineffective for deodorizing purposes. Thus, the provision ofoptimum compositions invariably requires the utilization of thedeodorizing agent in inordinately high concentrations in order to insurethe presence of suflicient quantities for the deodorizing problemconfronted. As will be readily apparent, practical as well as economicconsidera tions may well dictate against the advisability of employingthe deodorizing material in excess quantities.

In an effort to overcome or otherwise mitigate the foregoing and relateddisadvantages, considerable industrial activity has centered around theresearch and development of deodorizing agents specifically andadvantageously adapted for use in the preparation of aerosol spacedeodorant compositions such agents being characterized by exceptionalstability against the degradative effects of heat, humidity etc. Many ofthe remedial procedures heretofore promulgated are based upon the use ofone or more additional stabilizer compounds which purportedly serve toaugment or otherwise enhance the capacity of the deodorizing agent towithstand deleterious environments.

United States Patent ice Although some measure of success has beenexperienced with such techniques, the attendant disadvantages are oftenof such significance as to dictate resort to the use of alternativeprocedures. Thus, in many instances, the added cost involved provesprohibitive while in other cases, the stabilizing compound exhibits atendency to reduce the potency of the deodorizing agent. Moreover, it isoften found that the requisite compatibility of the involved ingredientscan be achieved only with difi'iculty.

In accordance with the discovery forming the basis of the presentinvention it has been ascertained that a relatively delimited class ofchemical compounds function to outstanding advantage in aerosolcompositions specifically adapted to perform a space-deodorizingfunction.

Thus, the primary object of the present invention resides in theprovision of aerosol deodorizing compositions wherein the foregoing andrelated disadvantages are eliminated or at least mitigrated to asubstantial degree.

Another object of the present invention resides in the provision ofaerosol deodorizing compositions having superior capability to dissipateor otherwise neutralize the effects of malodorous substances.

A further object of the present invention resides in the provision ofaerosol deodorizing compositions having exceptional stability againstthe degradative effects of heat, humidity and the like.

The attainment of the foregoing and related objects is made possible inaccordance with the present invention which in its broader aspectsincludes the provision of an aerosol deodorizing composition containingas essential ingredients (1) a liquefied, normally gaseous aerosolpropellant and (2) an organic peroxide having a half-life of at least 10hours at a temperature of C.

Compositions constituted in accordance with the present invention may beeffectively employed in connection with the suppression or obliterationof a wide variety of objectionable odors, including for example, themercaptan sulfide and amine odors associated with cooking, the pyridineodors associated with smoking, the valeric acid evolved duringperspiration etc. The treated air space would of course be renderednon-odorous or alternatively, pleasantly odorous, depending upon Whetheror not perfume ingredients are present in the aerosol deodorant. It isto be understood of course that perfuming agents comprise optionaladdenda in the compositions of the present invention. In addition,compositions formulated in accordance with the present invention have aminimal level of toxicity, being completely devoid of any tendency toirritate the eyes, nose, or throat. Moreover, such compositions do notyield unsightly films or residues on furniture, clothes or othersurfaces under ordinary conditions of use.

The organic peroxides contemplated for use herein may be represented forconvenience according to the following structural formula:

wherein when R is an alkyl group of from 2 to 8 carbon atoms, R isselected from the group consisting of aralkyl containing from 9 to 19carbon atoms, e.g., t-hutyl cumyl peroxide; peroxy alkyl containing from12 to 24 carbon atoms, e.g., 2,5-Di(T-butyl-peroxy)-2,5-dimethyl hexane;peroxy aralkyl containing from 16 to 29 carbon atoms, e.g.,1,4-Di(2-t-butyl-peroxy-isopropyl) benzene; peroxyalkynyl containingfrom 12 to 24 carbon atoms, e.g., 2,5- Di (t-butylperoxy)-2,5-dimethylhexyne-3; carbalkoxyalkyl, said alkoxy containing from 5 to 15 carbonatoms and said alkyl containing from 2 to 10 carbon atoms, e.g., n-Buty4,4-bis(t-butylperoxy)-valerate; and wherein when R is an aralakyl groupcontaining from 9 to 19 carbon atoms, R is also an aralkyl groupcontaining from 9 to 19 carbon atoms, e.g., dicumyl peroxide.

The peroxides contemplated for use in the practice of the presentinvention may properly be termed dialkyl proxides since each of theoxygens comprising the peroxide moiety is attached to an alkyl groupwhich in certain instances may be further substituted with groups ofthetype mentioned. Thus, the terms dial-kyl and alkyl as used in thecontext of the present invention are to be accorded a meaning andsignificance consistent with the foregoing definition. In any event, itwill be understood that the precise chemical structure of the dialkylperoxide is non-germane to a determination of particular species fallingwithin the contemplation of the present invention, the sole criteria tobe invoked in this regard being halflife as a function of temperature,namely, the dialkyl peroxide must be one having a half-life of at leasthours at 110 C.

As particular examples of organic peroxides falling within the ambit ofthe foregoing structural formula there may be mentioned in particularand without necessary limitation the following:

The propellant materials contemplated for use in the practice of thepresent invention may be selected from any of those materialsconventionally employed in the art for such purposes. It will beunderstood of course that Within the broad class of materials found tobe useful, certain members present special advantage from the standpointof flammability, toxicity, compatibility, etc. and thus propellantselection should be made having reference thereto. In any event, inaccordance with preferred practice, the propellant selected shoulddesirably exhibit minimal flammability and to this extent thehalogenated hydrocarbons are found to be particularly beneficial.Representative halogenated hydrocarbon propellants include, Withoutnecessary limitation, halogenated ethane, methane and mixtures thereof.Many of the halogenated hydrocarbons are commonly referred to in the artas Freons and Genetrons with specific examples includingdichlorodifluoromethane (Freon 12), dichlorotetrafluo- CompoundStructure n-Butyl 4,4-bls (t-butylperoxy)-valerate1,4-1)i(2-t-butylperoxy-isopropyl)benzene Dlcumyl peroxide2,5-Di(t-Butylperoxy)-2,5-dimethylhexane.

t-Butyl cumyl peroxl e 2,5-Di(t-butylperoxy) -2,5dlmethyl-hexyne-3 Ternerature C.) at which half-life is about 10 hours The concentration ofdialkyl peroxide employed is not roethane (Freon 114),trichlorotrifiuoroethane (Freon particularly critical, the salientrequirement being that such material be employed in amounts sufficientto effectively negotiate the odor problem at hand. Thus, for the vastmajority of applications, the dialkyl peroxide deodorizing agent may beemployed in relatively small amounts; in any event, optimum realizationof the improvements described herein is assured by the utilization ofthe dialkyl peroxide compound in concentrations ranging from about 0.01%to 5% by weight of aerosol composition with a range of 0.1% to 2.0%being particularly preferred. It will be understood that departures fromthe foregoing concentration values may be dictated in a particularcircumstance depending largely upon the requirements of the processor.Thus, should the odor problem presented by unusually sever, it may wellbe necessary to materially increase the concentration of dialkylperoxide. Thus, the aforementioned concentration ranges represnt thosevalues found to assure the obtention of optimum results for the vastmajority of deodorizing problems likely to be encountered. It willfurther be understood that the dialkyl peroxide may be employed inadmixtures comprising two or more. Again, the efficacy of so proceedinglies largely within the discretion of the processor.

As indicated previously, it is imperative that the dialkyl peroxideselected for use conform to predetermined requirements as regardshalf-life under elevated temperature conditions; thus, it is of criticalimportance that such material possess a half-life of at least 10 hoursat 110 C. Dialkyl peroxide compounds embraced by the foregoingdefinition are found not only to be exceptionally stable despitesubjection to severe conditions of temperature, humidity, etc., but, inaddition, prove highly effective as regards capacity to neutralizeoffensive odors despite their employment in concentrations approximatingbut a fraction of those found to be necessary with many of thedeodorizing compounds heretofore recommended. Thus, superior deodorizingefiiciency obtains despite the use of the dialkyl peroxide inconcentrations approximating for example, but one-tenth of thoseemployed with concentional space deodorants. The term half-life as usedin the context of the present invention has reference to the timerequired to decompose one-half of the peroxide originally presentaccording to the procedure described by D. S. Doehnert and O1 Maglli,Modern Plastics, Volume 36, No. 6, page 142 (1959).

113), trichloromonofluoromethane (Freon l1), heptafluoropropane, andoctafiuorocyclobutane as well as mixtures of two or more of theforegoing. Particularly preferred for use herein is a propellant blendcomprising from about 45% to about 55% trichloromonoiiuoromethane, theremainder comprising dichlorodiiluoromethane. It is sometimes found inpractice that a given halogenated hydrocarbon will possess a slightlydetectable odor under particular conditions of use. The use of suchmaterials should of course be avoided Where the possibility exists thatthe characteristic odor might possibly prove objectionable. Otherpropellant materials found to be suitable for use herein includehydrocarbons such as propane, isobutane, etc., although it should beunderstood that certain precautions must be exercised as regards the useof such materials in order to eliminate or at least minimize problemsassociated with flammability. Inorganic propellants such as nitrogen maylikewise be employed. However, the use of these materials invariablyrequires that the aerosol container ingredient be agitated prior to usein order to assure homogeneous intermixing of the propellant anddodorizing agent. In addition, it will be understood that the selectionof a particular propellant should be correlated with the type ofcontainer employed as well as the vapor pressure desired. Thus, thehydrocarbon type propellants are found to be particularly advantageousfrom the standpoint of permitting the maintenance of the optimum vaporpressure values.

The proportions of propellant employed are not particularly criticalapart from the obvious requirement that the amount selected besufiicient to permit substantially complete expulsion of the containeringredients in homogeneous form e.g., in the form of an intimatemixture. In general, it is found that the foregoing requirements may besatisfied by the use of the propellant material in quantities sufiicientto yield a container pressure within the range of about 30 pounds persquare inch absolute to about 115 pounds per square inch absolute undernormal conditions of use i.e., at about 70 F.

Other ingredients of an optional nature may likewise be included in theaerosol composition such as perfumes, antibacterial agents, auxiliarysolvents etc. and vapor pressure depressants to expedite pressureadjustment. Thus, methylene chloride and methyl chloroform etc. whichcomprise propellants also serve as auxiliary solvents and vapor pressuredepressants. Extender compounds such as typified by odorless mineralspirits, hexane etc. can likewise be employed, such materials serving assolvents for the dialkyl peroxide compound. The concentration of anysuch auxiliary ingredient may vary over a relatively wide range; thus,it is recommended practice to employ the liquid hydrocarbon dialkylperoxide solvent in concentra tions ranging from up to about 15% byweight of aerosol composition and preferably within the range of aboutto about 11%.

The following examples are given for purposes of illustration only andshould not be interpreted as necessarily constituting a limitation onthe present invention.

Example 1 The following composition is prepared:

Percent Dicumyl peroxide 0.25 Odorless mineral spirit 1 14.75Trichloromonofluoromethane 38.25 Dichlorodifluoromethane 46.75

water-white, clear and free of suspended matter being a mixture ofhydrocarbons having in a USTM distillation an initial boiling point nothigher than 410 F. having a Taglibue closed cup flash point of at least100 F. and upon distillation leaving a residue and charged to an aerosolcontainer fitted with 0.018 inch by 0.080 inch precision valves and0.023 inch buttons.

The aerosol composition thus prepared is compared with a commerciallyavailable space deodorant containing as deodorizing agents 2.5% oflauryl methacrylate and 020% of 3,5,5-trimethylhexanal.

The results of the comparison are tabulated as follows:

Total grams to Spray reach rate, odor end grams/ Formulation point sec.

Commercial spray 8. 6 1. 4 Instant spray 13. 7 l. 5

As the summarized data makes manifestly clear, the aerosol spacedeodorant composition containing the dialkyl peroxide compound provesmarkedly superior on the order of about to times as effective as thecommercial spray composition containing the lauryl methacrylate and3,5,5-trimethylhexanal.

Example 2 Example 1 is repeated except that the composition omits theodorless mineral spirits. Again, comparison of the respective aerosolcomposition establishes unequivocally the marked superiority of thedialkyl peroxide-containing formulation.

Examples 3-12 Examples 1 and 2 are repeated with the exception that thedicumyl peroxide is replaced in equivalent amounts with the following:

Ex. No. Dialkyl peroxide 3 and 4 n-butyl4,4-bis(=t-butylperoxy)-valerate.

5 and 6 1,4-di-(Z-t-butyperoxy-isopropyl) benzene.

7 and 8 t-butyl cumyl peroxide.

9 and 10 2,5-di-(t-butylperoxy)-2,5-dimethyl hexane.

11 and 12 2,5-di(t-butylperoxy)-2,5-dimethyl hexyne-3.

tafluoropropane, oc-tafluorocyclobutane, nitrous oxide, compressed air,carbon dioxide, argon as well as compatible mixtures comprising two ormore of such materials.

What is claimed is: 1. An aerosol air deodorizing composition consistingessentially of (l) a liquefied, normally gaseous propellant and (2) aneifective deodorizing amount of a dialkyl peroxide having a half-life ofat least 10 hours at C. and having the following structural formula:

wherein R is alkyl of from 2-8 carbon atoms or aralkyl of from 9-19carbon atoms; and when R is alkyl of from 2 to 8 carbon atoms, .R isselected from the group consisting of aralkyl containing from 9 to 19carbon atoms, peroxy alkyl containing from 12 to 24 carbon atoms, peroxyaralkyl containing from 16 to 29 carbon atoms, peroxyalkynyl containingfrom 12 to 24 carbon atoms and, carbalkoxyalkyl, said alkoxy containingfrom 5 to 15 carbon atoms and said alkyl containing from 2 to 10 carbonatoms; and when R is aralkyl containing from 9-l9 carbon atoms R is alsoaralkyl containing from 9- 19 carbons atoms; wherein each of the oxygenscomprising the peroxide moiety is attached to an alkyl p;

wherein said dialkyl peroxide is present in a concentration ranging fromabout 0.01% to 5.0% by weight of the aerosol composition; and whereinsaid propellant is present in quantities sufficient to yield a containerpressure within the range of about 30 lbs. per square inch absolute toabout lbs. per square inch absolute at about 70 F.

2. The aerosol composition according to Claim 1 wherein said propellantis a mixture of 45-55 percent trichloromonofiuoromethane and a balanceof dichlorodifluorometh-ane.

3. The aerosol composition according to Claim 1 wherein said dialkylperoxide is n-butyl 4,4-bis(tbutylperoxy)-valerate.

4. The aerosol composition according to Claim 1 said dialkyl peroxide is1,4-di'(2-t-butylperoxy-isopropyl) benzene.

5. The aerosol composition according to Claim 1 wherein said dialkylperoxide is dicumyl peroxide.

6. The aerosol composition according to Claim 1 wherein said dialkylperoxide is 2,5-di(t-butylperoxy)-2,5- dimethyl hexane.

7. The aerosol composition according to Claim 1 wherein said dialkylperoxide is t-butyl cumyl peroxide.

8. The aerosol composition according to Claim 1 wherein said dialkylperoxide is 2,5-di (t-butylperoxy)-2,5- dimethyl hexane-3.

9. The aerosol composition according to Claim 1 further containing fromabout 5% :to about 11% of odorless mineral spirits which is a solventfor the said dialkyl peroxide.

10. A method of deodorizing an enclosed air space which comprisesspraying into said space an air deodorizing amount of the compositionaccording to Claim 1.

References Cited UNITED STATES PATENTS 2,655,480 10/1953 Spitzer et a1.424-47 2,715,611 '8/1955 Weeks 21--55 2,879,284 3/ 1959 Divine et a1.260989 3,102,101 8/1963 Hawley et al 252- 305 3,250,724 5/1966 Kulka252- 305 D. TURNER, Primary Examiner U.S. Cl. X.R.

